Soot platelets and PAHs with an odd number of unsaturated carbon atoms and Π electrons: Theoretical study of their spin properties and interaction with ozone

PAHs made by an odd number of unsaturated carbon atoms and Π electrons (odd PAHs) have been detected in flames, and flank the more familiar even PAHs, having approximately the same quantitative importance, in particular for PAHs containing more than 25 carbon atoms. Similarly, soot platelets containing an odd number of carbon atoms can be reasonably assumed to form during combustion. PAHs are intended here as small models to investigate some of their local features. To this end, quantum mechanical calculations were also carried out on periodic models. The spin density patterns were found to be highly dependent on the PAH size and shape. PAHs and soot, once released in the environment, can undergo several oxidation processes. Ozone is then taken as a probe of the reactivity properties of some internal exposed portions of a platelet. A primary ozonide (PO) corresponds to an energy minimum, but the relevant concerted addition pathway does not exist, since a PO-like saddle point is second order. The reaction begins with a nonconcerted attack that produces a trioxyl radical (TR). Subsequent O2 loss from TR leaves either an epoxide with a Π-delocalized electron or a Π-delocalized oxepine, by cleavage of the ring carbon-carbon bond. The initial doublet spin multiplicity thus provides a description of the reaction surface unlike that for the internal reactivity of the closed shell even systems investigated in a previous work, even though the final functionalization is the same.